najoNanosystems: Physics, Chemistry, MathematicsНаносистемы: физика, химия, математика2220-80542305-7971Университет ИТМОnajo-1006Research ArticleСтатьиCubic ordered modification of titanium monoxide with structural vacancies on metal and nonmetal sublattices: electronic structure and stabilityKostenkoM. G.

620990 Pervomayskaya 91, Ekaterinburg

LukoyanovA. V.

620990 S. Kovalevskoy 18, Ekaterinburg

620002 Mira 19, Ekaterinburg

ZhukovV. P.

620990 Pervomayskaya 91, Ekaterinburg

RempelA. A.

620990 Pervomayskaya 91, Ekaterinburg

620002 Mira 19, Ekaterinburg

tel: +7 (343) 374 73 06, fax: +7 (343) 374 44 95

rempel@ihim.uran.ruInstitute of Solid State Chemistry, Ural Branch of the Russian Academy of SciencesRussian FederationInstitute of Metal Physics, the Ural Branch of the Russian Academy of Sciences; Ural Federal University named after the first President of Russia B. N. YeltsinRussian FederationInstitute of Solid State Chemistry, Ural Branch of the Russian Academy of Sciences; Ural Federal University named after the first President of Russia B. N. YeltsinRussian Federation20141508202554540545Copyright © Kostenko M.G., Lukoyanov A.V., Zhukov V.P., Rempel A.A., 20252025Kostenko M.G., Lukoyanov A.V., Zhukov V.P., Rempel A.A.Kostenko M.G., Lukoyanov A.V., Zhukov V.P., Rempel A.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://nanojournal.ifmo.ru/jour/article/view/1006

The electronic structure of the recently suggested cubic ordered phase Ti5O5(cub.) of titanium monoxide has been studied by means of accurate first-principles calculations within the density functional theory with pseudo-potential approach based on the plane wave basis. It was found that Ti5O5(cub.) is the only phase of titanium monoxide without p-d gap in the occupied states region. In this sense, calculated DOS’s of the cubic modification is closer to the experimental electronic spectrum of the ordered titanium monoxide than that of the well studied ordered monoclinic modification Ti5O5(mon.). The enthalpy of formation of Ti5O5(cub.) is higher than the enthalpy of Ti5O5(mon.) but is less than that of the disordered cubic phase TiO1.0.

vacanciesorderingtitanium monoxideelectronic structureThe authors thank A. A. Valeeva for advice provided and interest in this work. The study was financially supported by Ural Brunch of the Russian Academy of Sciences (Project No. 12-M-23-2001 and 14-31-NP-100) and by RFBR (research project No. 14-02-00636). Calculations were performed using ‘Uran’ supercomputer in the Institute of Mathematics and Mechanics UB RAS.ReferencesA. I. Gusev, A. A. Rempel, A. Magerl, Disorder and Order in Strongly Non-Stoichiometric Compounds. Transition Metal Carbides, Nitrides and Oxides, Springer, Berlin (2001).A. I. Gusev, A. A. Rempel, A. Magerl, Disorder and Order in Strongly Non-Stoichiometric Compounds. Transition Metal Carbides, Nitrides and Oxides, Springer, Berlin (2001).D. Watanabe et al. The ordered structure of TiO. Acta Cryst., 23, P. 307 (1967).D. Watanabe et al. The ordered structure of TiO. Acta Cryst., 23, P. 307 (1967).D. Watanabe, et al. Electron microscopic study on the structure of low temperature modification of titanium monoxide phase. In: L. Eyring, M. O’Keefe (Eds.). The Chemistry of Extended Defects in Non-Metallic Solids, North-Holland, Amsterdam, P. 238 (1970).D. Watanabe, et al. Electron microscopic study on the structure of low temperature modification of titanium monoxide phase. In: L. Eyring, M. O’Keefe (Eds.). The Chemistry of Extended Defects in Non-Metallic Solids, North-Holland, Amsterdam, P. 238 (1970).A.A. Valeeva, A.A. Rempel, A.I. Gusev. Ordering of cubic titanium Monoxide into Monoclinic Ti5O5. Inorg. Mater., 37 P. 603 (2001).A.A. Valeeva, A.A. Rempel, A.I. Gusev. Ordering of cubic titanium Monoxide into Monoclinic Ti5O5. Inorg. Mater., 37 P. 603 (2001).E. Hilti. Neue phasen im System Titan-Sauerstoff. Naturwissenschaften, 55, P. 130 (1968).E. Hilti. Neue phasen im System Titan-Sauerstoff. Naturwissenschaften, 55, P. 130 (1968).C. Leung et al. First-principles study of titanium oxides. Phys. Rev. B, 54 (11), P. 7857 (1996).C. Leung et al. First-principles study of titanium oxides. Phys. Rev. B, 54 (11), P. 7857 (1996).D.A. Andersson, P.A. Korzhavyi, B. Johansson. Thermodynamics of structural vacancies in titanium monoxide from first-principles calculations. Phys. Rev. B, 71, P. 144101-1 (2005).D.A. Andersson, P.A. Korzhavyi, B. Johansson. Thermodynamics of structural vacancies in titanium monoxide from first-principles calculations. Phys. Rev. B, 71, P. 144101-1 (2005).J. Graciani, A. M´arquez, Javier Fdez. Sanz. Role of vacancies in the structural stability of a–TiO: A firstprinciples study based on density-functional calculations. Phys. Rev. B, 72, P. 054117 (2005).J. Graciani, A. M´arquez, Javier Fdez. Sanz. Role of vacancies in the structural stability of a–TiO: A firstprinciples study based on density-functional calculations. Phys. Rev. B, 72, P. 054117 (2005).M.G. Kostenko et al. Vacancies in ordered and disordered titanium monoxide: Mechanism of B1 structure stabilization. J. Sol. State Chem., 204, P. 146 (2013).M.G. Kostenko et al. Vacancies in ordered and disordered titanium monoxide: Mechanism of B1 structure stabilization. J. Sol. State Chem., 204, P. 146 (2013).A.A. Valeeva et al. Identification of atomic Vacancies in titanium monoxide by electron microdiffraction and positron annihilation. Phys. Stat. Sol., 224 (b), R1 (2001).A.A. Valeeva et al. Identification of atomic Vacancies in titanium monoxide by electron microdiffraction and positron annihilation. Phys. Stat. Sol., 224 (b), R1 (2001).S. Bartkowski et al. Electron structure of titanium monoxide. Phys. Rev. B, 56, P. 10656 (1997).S. Bartkowski et al. Electron structure of titanium monoxide. Phys. Rev. B, 56, P. 10656 (1997).A.I. Gusev, A.A. Valeeva. Diffraction of electrons in the cubic Ti5O5 superstructure of titanium monoxide. JETP Letters, 96 (6), P. 364 (2012).A.I. Gusev, A.A. Valeeva. Diffraction of electrons in the cubic Ti5O5 superstructure of titanium monoxide. JETP Letters, 96 (6), P. 364 (2012).A.I. Gusev. New cubic superstructure of titanuim monoxide with double structure imperfection. J. Sol. State Chem., 199, P. 181 (2013).A.I. Gusev. New cubic superstructure of titanuim monoxide with double structure imperfection. J. Sol. State Chem., 199, P. 181 (2013).J.P. Perdew, et al., Generalized gradient approximation made simple. Phys. Rev. Lett., 77, P. 3865 (1996).J.P. Perdew, et al., Generalized gradient approximation made simple. Phys. Rev. Lett., 77, P. 3865 (1996).P. Giannozzi, et al. Quantum espresso: a modular and open-sourse software project for quantum simulation of materials. J. Phys. Condens. Matter, 21, P. 395502 (2009).P. Giannozzi, et al. Quantum espresso: a modular and open-sourse software project for quantum simulation of materials. J. Phys. Condens. Matter, 21, P. 395502 (2009).M.G. Kostenko, et al. Electronic structure of disordered titanium monoxide TiOy dependind on stoichiometry. JETP Letters, 95 (12), P. 647 (2012).M.G. Kostenko, et al. Electronic structure of disordered titanium monoxide TiOy dependind on stoichiometry. JETP Letters, 95 (12), P. 647 (2012).M.A. Korotin, et al. JETP Letters, 95 (12), P. 641 (2012).M.A. Korotin, et al. JETP Letters, 95 (12), P. 641 (2012).M.G. Kostenko et al. Effect of the long-range order in the vacancy distribution on the electronic structure of titanium monoxide TiO0.1. JETP Letters, 96 (8), P. 507 (2012).M.G. Kostenko et al. Effect of the long-range order in the vacancy distribution on the electronic structure of titanium monoxide TiO0.1. JETP Letters, 96 (8), P. 507 (2012).

The authors declare that there are no conflicts of interest present.